CN103145199A - Preparation method of cobalt oxide/graphene composite nano material - Google Patents
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Abstract
The invention relates to a preparation method of a cobalt oxide/graphene composite nano material, which is characterized by comprising the following steps: (1) preparing a 0.01-1.00 mol/L cobalt nitrate-organic fuel mixed solution, wherein the mol ratio of organic fuel to metal ions is 0.9-2; (2) preparing a 0.1-1.0 mg/ml graphene oxide dispersion solution; (3) calculating the volumes of the mixed solution obtained in the step (1) and the graphene oxide dispersion solution obtained in the step (2) according to the mass ratio of cobalt oxide to graphene in the designed product and the required preparation amounts, and mixing the mixed solution and the graphene oxide dispersion solution by ultrasonic to obtain a dispersion solution for atomization; (4) filling the dispersion solution obtained in the step (3) into an ultrasonic atomization device, carrying the generated atomized liquid drops into a 500-1100 DEG C pipe furnace by argon or nitrogen gas at the flow rate of 0.3-1.2 L/minute, and initiating solution combustion reaction; and (5) collecting the solid reaction product. The invention has the advantages of shorter technical procedure, simple synthesis equipment and continuous preparation process, can directly obtain the final powder product by one step, and can easily implement industrialized preparation.
Description
Technical field
The invention belongs to the material technology field, relate to the preparation method of composite nano materials.
Background technology
Tricobalt tetroxide (Co
3O
4) be a kind of transition metal oxide of important normal spine type structure, have the performances such as unique light, electricity, magnetic, electrochemistry, catalysis, except being applied to the traditional field such as superhard material, enamel beramic color, also be widely used in numerous frontiers such as pressure-sensitive gas sensor, catalyzer, ultracapacitor, flat-panel monitor, magneticsubstance and anode material for lithium-ion batteries.Co
3O
4Effect in these areas, except the effect that is subjected to the chemical property of material own, its microtexture (as grain size, particle size distribution and crystal morphology) is impact and the key parameter that determines its performance.Therefore, in recent years, high quality nano Co
3O
4The control synthetic technology of powder is owing to there being important using value to be subject to broad research.
KS Novoselov in 2004 and AK Geim etc. isolate stable Graphene (Graphene first, guide number) afterwards, discovery successively along with the light of a series of uniquenesses of Graphene, electricity, magnetic, thermal properties, caused that scientific circles pay close attention to greatly, become a large focus in current nano materials research field.Compare with carbon nanotube, the Graphene of two-dimentional monoatomic layer has theoretical specific surface area (2630 m of super large
2G
-1)Extremely special electronics/surface/adsorption property, good conductive and heat-conductive character and very high physical strength, chemistry and thermostability, and surface treatment is convenient, preparation cost is relatively cheap, therefore, Graphene has been showed wide application prospect in many fields such as catalysis, the energy, biology, environmental improvement and analyses.Due to the synergistic effect between Graphene and inorganic nano-particle, inorganic nano particle/graphite alkene composite nano materials shows excellent performance and the function of improvement, in recent years, and Co
3O
4The control preparation of/Graphene composite nano materials and performance study always current focus obtained in the lump positive progress.At present, Co
3O
4/ Graphene composite nano materials synthetic method mainly contains water/solvent-thermal method, liquid-control-precipitation, sol-gel method, sonochemistry method, microwave assisting method etc. the mesoporous Co of modification that refluxes and obtain as long-time in utilizations such as Xiaoling Yang
3O
4Microballoon has obtained GN with graphene oxide mixing self-assembly and has coated Co
3O
4(XL Yang, KC Fan, YH Zhu, et al. J
. Mater. Chem., 2012,22,17278 – 17283); C Xu etc. has synthesized Co in the hexanol system high-temperature backflow precipitator method 3 O 4 / Graphene web-like composite nano materials (C Xu, X Wang, JW Zhu, J. Mater. Chem., 2008,18,5625 – 5629); WW Zhou etc. adopt the two synthetic Co of step tensio-active agent auxiliary law
3O
4/ Graphene web-like composite nano materials (WW Zhou, JP Liu, T Chen, et al.
Phys. Chem. Chem. Phys., 2011,13:14462 – 14465); ZS Wu etc. take ammoniacal liquor as precipitation agent, obtain Co through precipitation and protection of inert gas calcination process in the isopropanol/water system
3O
4/ Graphene (ZS Wu, WC Ren, L Wen, et al.
ACS nano2010,6:3187 – 3194); S Qiang etc. adopt the microwave-assisted precipitation from homogeneous solution (PFHS) to obtain load C o take hexamethylenetetramine as precipitation agent
3O
4Flake graphite alkene composite structure (BJ Li, HQ Cao, J Shao,
Inorg. Chem.2011,50:1628 – 1632); The employings such as Y Liang precipitation has prepared in conjunction with the method for hydrothermal treatment consists the nano Co that loads on Graphene
3O
4Composite catalyst (Y Liang, Y Li, H Wang, et al.
Nature mater., 201110:780 – 786); LQTao etc. have obtained load on Graphene on Co through precipitation, hydrothermal treatment consists and thermal treatment take urea as precipitation agent in the ethanol/water system
3O
4Nanometer rod composite nano materials (LQTao, JT Zai, KX Wang, et al.
J Power Sources2012,202:230 – 235); It is worth noting that the employing hydrothermal methods such as XC Dong have been synthesized on the three-dimensional grapheme foam framework that vapour deposition process obtains has deposited Co
3O
4Nano wire, and the 3D Graphene composite nano materials of acquisition novelty (XC Dong,, H Xu, XW Wang, et al.
ACS nano, 2012,6:3206 – 3213).Due to the hydrophobicity of Graphene, can only be dispersed in the minority organic solvent, it is restricted as raw material, graphene oxide can be dispersed in water owing to containing oxygen-containing functional group, and easily a large amount of synthetic, becomes the most frequently used raw material.At present, in the method for various synthesizing graphite alkene base inorganic nano-composite materials, water/solvent-thermal method is being widely used in the synthetic graphene-based composite nano materials of various load oxide compounds, be characterized in need not subsequent heat treatment or calcining and just can form various nanostructures, but this method wants complete redox graphene often need add reductive agent, and the reaction times is longer, particularly forms nano composite oxide more difficult.Microwave heating is a kind of quick, even, energy-conservation type of heating, can be used for promoting reductive agent to the reduction of metal ion and graphene oxide, obtains fast M/GN, also can be used for promoting hydrolytic precipitation (SQ Chen, the Y Wang of metal ion
J. Mater. Chem., 2010,20:9735 – 9739).In sum, take graphene oxide as raw material, adopt the synthetic mertenyl inorganic nano composite material of solution original position synthetic technology, no matter be water/solvent-thermal method, liquid-control-precipitation, adopt water/solvent heat treatment, microwave-assisted no matter be, ultrasonic auxiliary, nearly all relate to washing, filter, the steps such as drying and calcining, the ubiquity synthesis step is many, time is long, and the solid-liquid separation difficulty is difficult to obtain the problems such as powder.
Summary of the invention
The objective of the invention is to overcome the defective of existing synthetic technology, a kind of novel method for preparing tricobalt tetroxide/Graphene composite nano materials is provided.
To achieve these goals, the present invention takes following technical scheme.
The preparation method of a kind of tricobalt tetroxide/Graphene composite nano materials is characterized in that comprising the following steps.
(1) compound concentration is the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 0.01 ~ 1.00 mol/L and the mixing solutions of organic-fuel, and wherein the mol ratio of organic-fuel and metal ion is 0.9 ~ 2.
(2) compound concentration is the graphene oxide dispersion liquid of 0.1 ~ 1.0 mg/ml.
(3) according to the quality of tricobalt tetroxide and Graphene in the design product required preparation amount when, calculate the volume of the graphene oxide dispersion liquid that mixing solutions that required step (1) obtains and step (2) obtain, then with both ultrasonic mixing, obtain the uniform dispersion for atomizing.
(4) dispersion liquid that step (3) is obtained is encased in ultrasonic atomizing device and atomizes, and it is in the tube furnace of 500 ~ 1100 ℃ that the atomizing droplet of generation is written into temperature by the argon gas of flow velocity 0.3 ~ 1.2 L/min or nitrogen, causes the solution combustion reaction; (5) collect solid and produce reactant, namely obtain tricobalt tetroxide/Graphene composite nano materials.
In step of the present invention (1), described cobalt nitrate solution can directly dissolve the hydration Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or utilize the oxyhydroxide of the oxide compound of the metal of nitric acid dissolve cobalt, cobalt, cobalt and the carbonate of cobalt in a kind of formulated, organic-fuel is a kind of in glycine, ethylene glycol or urea.
In step of the present invention (4), the silica tube internal diameter of tube furnace used is 16 mm, and external diameter is 20 mm; In ultrasonic atomizing device, the frequency of piezoelectric ceramic piece is 1.7 MHz or 2.4 MHz.
In step of the present invention (5), the collection of solid reaction product can be adopted cloth envelop collector or electrostatic precipitator, also can select monocrystalline silicon piece, Copper Foil, and silica glass, simple glass is collected as the cooling deposition of substrate.
for the problem of generally depositing in above-mentioned original position synthetic technology, based on graphene oxide and organic-fuel and the metal-salt dispersion system that dispersion energy formation has certain stability in water, the present invention is integrated solution combustion method and spray pyrolysis, one step quick tricobalt tetroxide/a kind of novel method of Graphene composite nano materials---spray burning method has been proposed innovatively, between Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in this method atomizing droplet and organic-fuel and graphene oxide functional group under tube furnace interior heat amount causes, redox reaction will occur, the ie in solution combustion reactions, complete that the original position of tricobalt tetroxide on Graphene generates and the reduction of Graphene one step.It is synthetic that method of the present invention has a step serialization, preparation time is short, need not to add reductive agent and subsequent heat treatment, there is not solid-liquid separation, directly obtain the distinguishing features such as powder, the new way of simple, quick, low-cost a, less energy-consumption will be provided for the commercialization of tricobalt tetroxide/mertenyl composite nano materials from now on is synthetic.
Clear superiority of the present invention is.
1, merge solution combustion method and spray pyrolysis advantage separately.
2, technical process is simple, there is no washing, solid-liquid separation, the process of drying and subsequent heat treatment, and a step directly obtains final powder product.
3, to be easy to a large amount of synthetic graphene oxides as raw material, the vulcanizing agent that uses is again reductive agent simultaneously.
Serialization is synthetic, and preparation time is short, and synthesis device is simple, is easy to realize preparation of industrialization.
Description of drawings
Fig. 1 is the X-ray diffractogram of Comparative Examples.
Fig. 2 is the transmission electron microscope photo of Comparative Examples.
Fig. 3 is the electron diffraction photo of Comparative Examples.
Fig. 4 is the transmission electron microscope photo of embodiment 1.
Fig. 5 is the high-resolution-ration transmission electric-lens photo of embodiment 1.
Fig. 6 is the electron diffraction photo of embodiment 1.
Fig. 7 is the transmission electron microscope photo of embodiment 2.
Fig. 8 is the transmission electron microscope photo of embodiment 3.
As shown in Figure 1, coincideing of the X-ray diffractogram of comparative example and Graphene shows to have obtained processing through high temperature spray-drying that graphene oxide is by thermal reduction; As shown in Figure 2, comparative example is rolled state, above any particle of load, what obtain is pure Graphene; The electron diffraction photo of comparative example in Fig. 3 shows that also product is pure Graphene; Fig. 4 is the transmission electron microscope photo of embodiment 1, forming sharp contrast with Fig. 2 is to be clear that Graphene is bulk, the above's load equably nanoparticle, has formed the three-dimensional grapheme composite nanostructure, and this two-dirnentional structure from water/solvent-thermal method product is obviously different; Fig. 5 is the high-resolution-ration transmission electric-lens photo of embodiment 1, and lattice clearly, show that the particle that loads on Graphene is nanocrystal as we can see from the figure; The electron diffraction photo of embodiment 1 from Fig. 6 can be seen the sparse diffraction spot that distributing on Graphene feature electron diffraction ring, and this is mainly because the charge capacity of tricobalt tetroxide is very low; Fig. 7 and Fig. 8 are respectively the transmission electron microscope photos of embodiment 2 and 3, can see along with charge capacity increases the number of particles showed increased.
Embodiment
The present invention further illustrates by following Comparative Examples and embodiment.
Comparative Examples.
The 200 ml 0.5 ultrasonic mixing of the mg/ml graphene oxide solution 20min that prepare, mixing solutions pack in band circulating cooling ultrasonic atomizing device.Setting nitrogen flow rate is 0.8 L/min, opening the piezoelectric ceramic piece frequency is the atomisation unit of 2.4 MHz, and the drop of generation is written into the stove formula pipe of 800 ℃ by nitrogen, causes the solution combustion reaction, the solid product that generates deposits the collection sample by the monocrystalline silicon piece that is placed on the tube furnace exit end.
Take 30 mg glycine, adding 8 ml concentration is in the cobalt nitrate solution of 0.06 mol/L, ultrasonic mixing, graphene oxide suspension 100 ml that dropwise add 0.5 mg/ml, ultrasonic mixing, mixed solution is packed into be with in the circulating cooling ultrasonic atomizing device, setting nitrogen flow rate is 0.8 L/min, opening the piezoelectric ceramic piece frequency is the atomisation unit of 2.4MHz, the drop that produces is written into the stove formula pipe of 800 ℃ by nitrogen, cause the solution combustion reaction, the solid product of generation deposits the collection sample by the monocrystalline silicon piece that is placed on the tube furnace exit end.
Embodiment 2.
Take 60 mg glycine, adding 15 ml concentration is in the cobalt nitrate solution of 0.06 mol/L, ultrasonic mixing, graphene oxide suspension 100 ml that dropwise add 0.5 mg/ml, ultrasonic mixing, mixed solution is packed into be with in the circulating cooling ultrasonic atomizing device, setting nitrogen flow rate is 0.8 L/min, opening the piezoelectric ceramic piece frequency is the atomisation unit of 2.4MHz, the drop that produces is written into the stove formula pipe of 800 ℃ by nitrogen, cause the solution combustion reaction, the solid product of generation deposits the collection sample by the monocrystalline silicon piece that is placed on the tube furnace exit end.
Embodiment 3.
Take 115 mg ethylene glycol, adding 25ml concentration is in the cobalt nitrate solution of 0.06 mol/L, ultrasonic mixing, graphene oxide suspension 100 ml that dropwise add 0.5 mg/ml, ultrasonic mixing, mixed solution is packed into be with in the circulating cooling ultrasonic atomizing device, setting nitrogen flow rate is 0.8 L/min, opening the piezoelectric ceramic piece frequency is the atomisation unit of 2.4MHz, the drop that produces is written into the stove formula pipe of 800 ℃ by nitrogen, cause the solution combustion reaction, the solid product of generation deposits the collection sample by the monocrystalline silicon piece that is placed on the tube furnace exit end.
Claims (2)
1. the preparation method of tricobalt tetroxide/Graphene composite nano materials is characterized in that comprising the following steps:
(1) compound concentration is the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 0.01 ~ 1.00 mol/L and the mixing solutions of organic-fuel, and wherein the mol ratio of organic-fuel and metal ion is 0.9 ~ 2;
(2) compound concentration is the graphene oxide dispersion liquid of 0.1 ~ 1.0 mg/ml;
(3) according to the quality of tricobalt tetroxide and Graphene in the design product required preparation amount when, calculate the volume of the graphene oxide dispersion liquid that mixing solutions that required step (1) obtains and step (2) obtain, then with both ultrasonic mixing, obtain the uniform dispersion for atomizing;
(4) dispersion liquid that step (3) is obtained is encased in ultrasonic atomizing device and atomizes, and it is in the tube furnace of 500 ~ 1100 ℃ that the atomizing droplet of generation is written into temperature by the argon gas of flow velocity 0.3 ~ 1.2 L/min or nitrogen, causes the solution combustion reaction; (5) collect solid and produce reactant, namely obtain tricobalt tetroxide/Graphene composite nano materials;
Cobalt nitrate solution described in step (1) be directly dissolve the hydration Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or utilize the oxyhydroxide of oxide compound, cobalt of metal, the cobalt of nitric acid dissolve cobalt and the carbonate of cobalt in a kind of formulated; Organic-fuel is a kind of in glycine, ethylene glycol or urea;
In step (4), the silica tube internal diameter of tube furnace used is 16 mm, and external diameter is 20 mm; In ultrasonic atomizing device, the frequency of piezoelectric ceramic piece is 1.7 MHz or 2.4 MHz.
2. preparation method according to claim 1, is characterized in that in step (5), and cloth envelop collector or electrostatic precipitator are adopted in the collection of solid reaction product, perhaps select monocrystalline silicon piece, Copper Foil, and silica glass, simple glass is collected as the cooling deposition of substrate.
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CN103935989A (en) * | 2014-04-09 | 2014-07-23 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene by means of flammable solvent reduction |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102050485A (en) * | 2010-12-29 | 2011-05-11 | 中南大学 | Preparation method of high-density spherical barium titanate powder particles |
US20120064409A1 (en) * | 2010-09-10 | 2012-03-15 | Aruna Zhamu | Graphene-enhanced anode particulates for lithium ion batteries |
-
2013
- 2013-03-08 CN CN201310074309.0A patent/CN103145199B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120064409A1 (en) * | 2010-09-10 | 2012-03-15 | Aruna Zhamu | Graphene-enhanced anode particulates for lithium ion batteries |
CN102050485A (en) * | 2010-12-29 | 2011-05-11 | 中南大学 | Preparation method of high-density spherical barium titanate powder particles |
Non-Patent Citations (1)
Title |
---|
徐志军等: "喷雾热分解合成技术及其在材料研究中的应用", 《无机材料学报》 * |
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